- Catalyst Poisoning Phenomenon in Phase Transfer Catalysis: Effect of Aqueous Phase Concentration
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Catalyst poisoning was studied in the phase transfer-catalysed esterification of alkyl chlorides by sodium formate; the poisoning effect is minimized by use of highly concentrated formate solutions where high conversion and first order kinetics are observed.
- Sasson, Yoel,Zahalka, Hayder Ali
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- N,S-Dimethyldithiocarbamyl oxalates as precursors for determining kinetic parameters for oxyacyl radicals
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N,S-Dimethyldithiocarbamyl oxalates (e.g.6, 10) are novel, readily prepared precursors to alkyloxyacyl radicals 1 that are more suitable for kinetic studies than existing precursors; 10 has allowed the determination of accurate rate data for the cyclization of the butenyloxyacyl radical 5 (kc = 1.2 × 107 s-1 at 21 °C). This journal is
- Kyne, Sara H.,Schiesser, Carl H.
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- Lipase-catalyzed transesterification of ethyl formate to octyl formate
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The preparation of octyl formate via lipase-catalyzed transesterification of ethyl formate with 1-octanol is demonstrated. To shift the equilibrium of the reaction, ethyl formate was added in surplus but could be partially recovered for subsequent reactions. The same was true for the biocatalyst (Novo435), which could be reused at least 27 times. This method gives simple access to a hydrophobic formic acid ester, which can be used as a reactive organic phase in biocatalytic redox reactions. The enzymatically prepared octyl formate can be utilized by formate dehydrogenase to regenerate NADH from NAD+.
- Janssen, Leonie M.G.,Van Oosten, Remco,Paul, Caroline E.,Arends, Isabel W.C.E.,Hollmann, Frank
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- Method for preparing formate-type compound
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The invention discloses a method for preparing a formate-type compound. The method comprises the following steps of: adopting an alcohol-type compound and 1,3-dihydroxyacetone as reaction raw materials, and under the existence of a composite catalyst and an oxidant, reacting for 2-48 hours in a reaction medium in a reactor at a reaction temperature of 25-100 DEG C so as to obtain the formate-typecompound. The method disclosed by the invention is simple, and is mild in reaction condition, and by the method, a target product can be obtained by low cost and high yield; the used catalyst has highcatalytic activity, and is easily separated from a reaction system to be repeatedly used; the whole process is environment-friendly, and the reaction raw material (1,3-dihydroxyacetone) is easily converted from a side product (glycerol) of biodiesel, so that the utilization of the glycerol is promoted.
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Paragraph 0039; 0047; 0048
(2018/07/30)
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- Method of using swelling-able acidic poly(ionic liquid) to catalyze esterification between formic acid and alkenes to prepare formate
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The invention discloses a method of using swelling-able acidic poly(ionic liquid) to catalyze esterification between formic acid and alkenes to prepare formate. According to the method, an acidic poly(ionic liquid) that can swell in formic acid is synthesized at first; 1-vinyl-3-alkyl imidazolium bromine salt ionic liquid and sodium acrylate are taken as the copolymerization monomers, and throughfree radical polymerization and acidification that uses an acid with an equal molar weight, the poly(ionic liquid) is prepared. The poly(ionic liquid) is taken as a catalyst to catalyze the esterification reactions between formic acid and alkenes; the catalytic activity of the poly(ionic liquid) is equal to that of a homogeneous catalyst and the selectivity is higher than that of a homogeneous catalyst or a heterogeneous catalyst. The swelling-able acidic poly(ionic liquid) is used to catalyze the esterification reactions between formic acid and alkenes, the characteristic that the poly(ionicliquid) can swell in formic acid is utilized, the poly(ionic liquid) is fully dispersed in the substrate, at the same time, the active centers of the acid are immobilized on the poly(ionic liquid), thus the active centers can fully contact with the substrate, and the catalytic efficiency is largely improved.
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Paragraph 0029; 0030; 0031; 0033; 0034; 0042; 0043-0046
(2018/11/04)
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- Acidic ionic liquid based UiO-67 type MOFs: A stable and efficient heterogeneous catalyst for esterification
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A facile strategy for the synthesis of acidic ionic liquid based UiO-67 type MOFs was developed in this study. Br?nsted acids (H2SO4, CF3SO3H and hifpOSO3H (hexafluoroisopropyl sulfuric acid)) were introduced into UiO-67-bpy (bpy = 2,2′-bipyridine-5,5′-dicarboxylic acid) frameworks by reacting with bipyridyl nitrogen to introduce the properties of an acidic ionic liquid into the frameworks. The prepared catalysts, denoted as UiO-67-HSO4, UiO-67-CF3SO3 and UiO-67-hifpOSO3, were characterized by XRD, SEM, FT-IR, EA, TGA and N2 adsorption-desorption studies. The relatively high surface area was still maintained and acidic active groups were uniformly dispersed in the frameworks. The catalytic performance of UiO-67-HSO4, UiO-67-CF3SO3 and UiO-67-hifpOSO3 was evaluated by the esterification of acetic acid with isooctyl alcohol. The prepared catalysts showed good catalytic activities in the esterification, of which UiO-67-CF3SO3 gave the maximum isooctyl alcohol conversion of 98.6% under optimized conditions. The catalyst could be reused five times without a significant decrease in the conversion of isooctyl alcohol, and almost no active species were leached, indicating the excellent stability and reusability of the catalyst. Our study provides one effective way to synthesize heterogeneous acidic ionic liquid catalysts consisting of isolated, well defined acidic groups that will probably attract interest in acid catalyst chemistry.
- Xu, Zichen,Zhao, Guoying,Ullah, Latif,Wang, Meng,Wang, Aoyun,Zhang, Yanqiang,Zhang, Suojiang
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p. 10009 - 10016
(2018/03/23)
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- Ruthenium-Catalyzed Synthesis of Dialkoxymethane Ethers Utilizing Carbon Dioxide and Molecular Hydrogen
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The synthesis of dimethoxymethane (DMM) by a multistep reaction of methanol with carbon dioxide and molecular hydrogen is reported. Using the molecular catalyst [Ru(triphos)(tmm)] in combination with the Lewis acid Al(OTf)3resulted in a versatile catalytic system for the synthesis of various dialkoxymethane ethers. This new catalytic reaction provides the first synthetic example for the selective conversion of carbon dioxide and hydrogen into a formaldehyde oxidation level, thus opening access to new molecular structures using this important C1source.
- Thenert, Katharina,Beydoun, Kassem,Wiesenthal, Jan,Leitner, Walter,Klankermayer, Jürgen
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supporting information
p. 12266 - 12269
(2016/10/13)
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- Formamides as Lewis Base Catalysts in SNReactions—Efficient Transformation of Alcohols into Chlorides, Amines, and Ethers
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A simple formamide catalyst facilitates the efficient transformation of alcohols into alkyl chlorides with benzoyl chloride as the sole reagent. These nucleophilic substitutions proceed through iminium-activated alcohols as intermediates. The novel method, which can be even performed under solvent-free conditions, is distinguished by an excellent functional group tolerance, scalability (>100 g) and waste-balance (E-factor down to 2). Chiral substrates are converted with excellent levels of stereochemical inversion (99 %→≥95 % ee). In a practical one-pot procedure, the primary formed chlorides can be further transformed into amines, azides, ethers, sulfides, and nitriles. The value of the method was demonstrated in straightforward syntheses of the drugs rac-Clopidogrel and S-Fendiline.
- Huy, Peter H.,Motsch, Sebastian,Kappler, Sarah M.
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supporting information
p. 10145 - 10149
(2016/08/16)
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- Deep eutectic solvent choline chloride·2CrCl3·6H2O: An efficient catalyst for esterification of formic and acetic acid at room temperature
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A highly efficient and selective method for esterification of formic and acetic acid with alcohols has been achieved at room temperature, with the choline chloride (ChCl)/chromium(iii) chloride hexahydrate (CrCl3·6H2O) deep eutectic solvent as a catalyst. High yields and good selectivities of organic esters are obtained using DES [ChCl][CrCl3·6H2O]2 with the molar ratio 5:1 (carboxylic acids:alcohols) at room temperature in 24 h. The ease of recovery and reusability of DES with high catalytic activity makes this method efficient and practical.
- Cao, Jin,Qi, Bin,Liu, Jun,Shang, Yuhan,Liu, Huiwen,Wang, Wenjing,Lv, Jia,Chen, Zhiyan,Zhang, Haibo,Zhou, Xiaohai
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p. 21612 - 21616
(2016/03/08)
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- Method of manufacturing imidoyl diazidosulfochloride compd. various compd. and manufacturing method of using the same
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PROBLEM TO BE SOLVED: To provide a new production method for synthesizing an imidoyl chloride compound dispensing with chlorination agents having poor handleability, to provide a method for producing various compounds in high yield and purity by using the imidoyl chloride compound, and to provide a method for isolating the imidoyl chloride compound in high efficiency and purity from a mixture of the imidoyl chloride compound and a phthalic anhydride compound.SOLUTION: The method for producing the imidoyl chloride compound comprises reaction of a specific amide compound with a specific phthaloyl chloride compound to produce a specific imidoyl chloride compound.
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Paragraph 0070
(2016/12/16)
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- Tribromoisocyanuric acid (TBCA) as a mild and metal free catalyst for the acetylation and formylation of hydroxyl groups under solvent free conditions
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A convenient approach for acetylation and formylation of various types of alcohols and phenols with acetic anhydride and formic acid in the presence of Tribromoisocyanuric acid (TBCA) as catalyst is reported. The reactions were carried out under solvent-free condition and in good to high yields at room temperature. This present method is featured with relatively mild reaction conditions, simple operation, broad substrate scope, clean work-up, short reaction times, good to high yields, excellent selectivity and also avoids tedious purifications and the use of toxic reagents.
- Hekmatian, Zahra,Khazaei, Ardeshir
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p. 1565 - 1570
(2016/01/26)
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- 2-(Sulfooxy)propane-1,2,3-tricarboxylic acid as novel and versatile catalyst for the formylation of alcohols and amines using ethyl formate under neat conditions
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2-(Sulfooxy)propane-1,2,3-tricarboxylic acid (supported on silica gel) has been introduced as novel and green catalyst for the formylation of alcohols and amines with ethyl formate, as mild formylation agent, under neat conditions at room temperature.. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
- Ghorbani-Choghamarani, Arash,Akbaripanah, Ziba
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experimental part
p. 450 - 453
(2012/06/04)
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- Silica-bonded N-propyl sulfamic acid as an efficient catalyst for the formylation and acetylation of alcohols and amines under heterogeneous conditions
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A simple and efficient procedure for the preparation of silica-bonded N-propyl sulfamic acid (SBNPSA) by the reaction of 3-aminopropylsilica (1) and chlorosulfonic acid in chloroform is described. This solid acid is employed as a new catalyst for the formylation of alcohols and amines with ethyl formate under mild and heterogeneous conditions at room temperature with good to excellent yields. Also, SBNPSA catalyzed acetylation of various alcohols and amines with acetic anhydride at room temperature.
- Niknam, Khodabakhsh,Saberi, Dariush
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experimental part
p. 5210 - 5214
(2009/12/06)
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- Silica sulfuric acid and AI(HSO4)3: As efficient catalysts for the formylation of alcohols by using ethyl formate under heterogeneous conditions
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A mixture of ethyl formate and a catalytic amount of silica sulfuric acid or Al(HSO4)3 as suitable formylating systems can formylate various alcohols to their corresponding formate ester derivatives under mild, nearly neutral and heterogeneous conditions at room temperature with good to excellent yields.
- Zolfigol, Mohammad Ali,Chehardoli, Gholamabbas,Dehghanian, Mina,Niknam, Khodabakhsh,Shirini, Farhad,Khoramabadi-Zad, Ahmad
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experimental part
p. 885 - 889
(2009/12/04)
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- Selective aerobic oxidation in supercritical carbon dioxide catalyzed by the H5PV2Mo10O40 polyoxometalate
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Selective aerobic oxidation of benzylic alcohols and of activated aromatic hydrocarbons occurs in supercritical CO2 as reaction medium using H5PV2Mo10O40 as a quasi-heterogeneous catalyst without further additives or co-solvents; efficient recycling is possible and no metal leaching is detectable in the product stream. The Royal Society of Chemistry 2006.
- Maayan, Galia,Ganchegui, Benjamin,Leitner, Walter,Neumann, Ronny
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p. 2230 - 2232
(2007/10/03)
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- Corona-induced photoxidation of alcohols and hydrocarbons over TiO 2 in the absence of a UV light source - A novel and environmentally friendly method for oxidation
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Corona-induced photooxidation is a novel oxidation methodology for the efficient oxidation of alcohols and hydrocarbons utilizing the advantage of both the high oxidizing power of ozone formed in the reactor as well as the photooxidation capability of the UV light generated during the corona discharge. The Royal Society of Chemistry 2005.
- Pillai, Unnikrishnan R.,Sahle-Demessie, Endalkachew
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p. 2256 - 2258
(2007/10/03)
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- Cerium polyoxometalate as a reusable catalyst for acetylation and formylation of alcohols
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Efficient esterification of primary and sterically-hindered secondary or tertiary alcohols with acetic anhydride was achieved in the presence of ammonium decatungestocerate(IV) icosahydrate, (NH4)8[CeW 10O36]·OH2O, as catalyst in high yields. Primary and secondary alcohols were also converted to their corresponding acetates and formates with acetic acid and ethyl formate in the presence of this catalyst. Easy work-up, non-toxicity, reusability, and stability of the catalyst are noteworthy advantages of this method. Springer-Verlag 2004.
- Mirkhani, Valiollah,Tangestaninejad, Shahram,Moghadam, Majid,Yadollahi, Bahram,Alipanah, Ladan
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p. 1257 - 1263
(2007/10/03)
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- Vilsmeier-Haack Reagents. Novel Electrophiles for the One-Step Formylation of O-Silylated Ethers to O-Formates
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Various O-silylated substrates were effectively converted in one-step to their corresponding O-formates using electrophilic racemic and homochiral Vilsmeier-Haack reagents. Reactivity trends of these transformations were examined that, specifically, empha
- Lellouche, Jean-Paul,Kotlyar, Vadim
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p. 564 - 571
(2007/10/03)
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- Iron perchlorate on silica gel as multi-purpose reagent for catalysis of closure and rupture of carbon-oxygen bond in epoxides, alcohols, and esters
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Aliphatic alcohols and water in the presence of catalytic amounts of Fe3+ ion introduced as iron(III) perchlorate on silica gel carrier perform efficient regiospecific opening of an epoxy ring. Carbon acids esterification with various type alcohols was carried out using the system Fe(ClO4)3-silica gel in dichloromethane under conditions excluding solvolysis. Acetylation and formylation of alcohols was performed by efficient transesterification with ethyl acetate and ethyl formate.
- Salechi,Khodaei,Ghareghani,Motlagh
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p. 794 - 796
(2007/10/03)
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- The fragmentation of alkoxychlorocarbenes in hydrocarbon solvents and in low temperature argon matrixes
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Alkoxychlorocarbenes (ROCCl, R = benzyl, cyclohexyl, and 1-octyl) were generated from the corresponding diazirines in acetonitrile, dichloroethane, benzene, cyclohexane, and pentane solutions at 25°C, and the fragmentations of these carbenes were studied. A prominent product was phenacyl chloride (PhCH2CoCl), a formal rearrangement product of the carbene. In polar solvents, the two fragmentation transition states for CH3OCCl and C2H5OCCl were stabilized to the point where cis-trans isomerization, loss of CO, and concerted loss of CO + Cl all have similar activation energies. In less polar solvents, such as dichloroethane, heterolytic cleavage was probably not competitive.
- Moss, Robert A.,Ma, Yan,Zheng, Fengmei,Sauers, Ronald R.,Bally, Thomas,Maltsev, Alexander,Toscano, John P.,Showalter, Brett M.
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p. 12280 - 12291
(2007/10/03)
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- Bi(III) salts as new catalysts for the selective conversion of trimethylsilyl and tetrahydropyranyl ethers to their corresponding acetates and formates
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Bi(III) salts such as BiCl3, Bi(TFA)3 and Bi(OTf)3 were found to be efficient catalysts for the transformation of trimethylsilyl (TMS) and tetrahydropyranyl (THP) ethers to their corresponding acetates and formates with acetic acid and ethyl formate. Selective acetylation and formylation of TMS and THP ethers of alcohols in the presence of phenolic TMS and THP ethers make this method a useful and practical procedure in organic synthesis.
- Mohammadpoor-Baltork,Khosropour
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p. 2433 - 2439
(2007/10/03)
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- A convenient and chemoselective acetylation and formylation of alcohols and phenols using acetic acid and ethyl formate in the presence of Bi(III) salts
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A variety of alcohols are acetylated and formylated efficiently with acetic acid and ethyl formate in the presence of catalytic amounts of Bi(III) salts such as BiCl3, Bi(TFA)3 and Bi(OTf)3. BiCl3 and Bi(OTf)3 are also effective catalysts for acetylation of phenols. All of these catalysts are ineffective in formylation of phenols. Selective acetylation and formylation of alcohols in the presence of phenols is an additional advantage of this procedure.
- Mohammadpoor-Baltork,Khosropour,Aliyan
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p. 280 - 282
(2007/10/03)
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- Novel catalytic acetylation and formylation of alcohols with potassium dodecatungstocobaltate trihydrate (K5CoW12O40·3H2O)
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Acetylation and formylation reactions of alcohols with ethyl acetate, acetic acid and ethyl formate were catalyzed with potassium dodecatungstocobaltate trihydrate (K5CoW12O40·3H2O) in a mild, efficient and convenient method with high to excellent yields.
- Habibi, Mohammad H,Tangestaninejad, Shahram,Mirkhani, Valiollah,Yadollahi, Bahram
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p. 8333 - 8337
(2007/10/03)
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- Preparation of formate esters from O-TBDMS/O-TES protected alcohols. A one-step conversion using the Vilsmeier-Haack complex POCl3/DMF
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O-tert-Butyldimethylsilylated (O-TBDMS) or O-triethylsilylated (O-TES) alcohols were converted in one step to their corresponding formates under Vilsmeier-Haack conditions (POCl3/DMF). The scope and limitations of this novel reaction for interconverting alcohol protecting groups are described.
- Koeller, Sylvain,Lellouche, Jean-Paul
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p. 7043 - 7046
(2007/10/03)
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- Conversion of trimethylsilyl ethers to acetyl or formyl esters with TiCl4
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A simple method is described for the efficient conversion of trimethylsilyl ethers to their corresponding acetyl and formyl esters in refluxing ethyl acetate or ethyl formate in the presence of TiCl4.
- Iranpoor, Nasser,Zeynizadeh, Behzad
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p. 2123 - 2128
(2007/10/03)
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- Catalytic esterification of alcohols, carboxylic acids and transesterification reactions with cerium(IV) triflate
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Esterification reactions of alcohols with acetic, chloroacetic, trifluoroacetic, propionic, stearic, and benzoic acids were catalyzed with Ce(OTf)4 in a solvent or under solvent-free conditions with high yields. The formylation and acetylation of primary and secondary alcohols were also easily achieved in ethyl formate and ethyl acetate. A high retention of the configuration was observed in the acetylation and formylation of (-)-menthol.
- Iranpoor, Nasser,Shekarriz, Marzieh
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p. 455 - 458
(2007/10/03)
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- Selective acetylation of primary alcohols: Acetyl and formyl transfer reactions with copper(II) salts
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The efficient esterification of primary and secondary alcohols in acetic acid was achieved in the presence of Cu(NO3)2. 3H20 in high yields. Selective acetylation of primary in the presence of secondary hydroxyl groups in excellent yields were performed in EtOAc. Formylation of primary and secondary alcohols was also achieved easily in ethyl formate. High retention of configuration was observed in the acetylafion and formylation of (-) menthol in the presence of Cu(NO3)2. 3H20 and Cu(OAC)2. H2O.
- Iranpoor,Firouzabadi,Zolfigol
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p. 1923 - 1934
(2007/10/03)
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- Conversion of alkyl halides into the corresponding alcohols under mild reaction conditions
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Reaction of primary, cyclopentyl, allyl and arylmethyl halides, but not an acyclic secondary halide or a tertiary halide, in acetone or tetrahydrofuran with the formate form of a commercial anion exchange resin gave formate esters in good yields. The formates were hydrolysed efficiently to the corresponding alcohols by a brief treatment with hydrochloric acid. Reaction of primary alkyl bromides or iodides, secondary alkyl bromides, cinnamyl and arylmethyl halides in tetrahydropyran or 1,4-dioxane with the bicarbonate form of the same anion-exchange resin gave the corresponding alcohols directly in good yields. This latter reaction can be carried out successfully in the presence of ester or amide groups.
- Ruddick, Clare L.,Hodge, Philip,Houghton, Mark P.
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p. 1359 - 1362
(2007/10/03)
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- Amides as Nucleophiles: Reaction of Alkyl Halides with Amides or with Amides and Water. A New Look at an Old Reaction
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Heating of formamide with an alkyl halide (with or without water) affords a mild, nonhydrolytic, high-yield synthesis of alcohols and formate esters.Yet the way in which substitution on the alkyl halide actually occurs remains obscure.To explore this question, thermal reaction of 1-bromooctane (1a) with formamides (HC(O)NHR, R=H, Me; 2a, 2b) was studied quantitatively.Major products are 1-octanol (3) and n-octyl formate (5); minor products are 1-octene (4), di-n-octyl ether (6), and N-octylformamide (7, from 2a, only).Solid coproduct is HC(=NR)NHR + Br(1-) (e.g., 8a, R=H, methanimidamide hydrobromide).Analogously, 1a and N-methylformamide (2b) give alkylated products 3,5, and 6 along with 8b (R=Me). 1-Iodooctane (1b) reacts similarly.Probe samples show that 1-octanol (3) is first formed, followed by 5 and 6.Occurence of 8a-c is key to a mechanistic interpretation of the reaction.An imidate ("salt I"), e.g., from 1a and 2b, is first formed and reacts with amide 2b to give and 3.Now alcohol 3 is converted to ester 5 and 8b by reaction with this same formylamidine.Water, if present, adds to the imidate and gives a new tetrahedral intermediate that cleaves to ester 5 and amide salt, RNH3X.Analogous reaction steps are proposed to generate side products 4, 6, and 7.Alkylation of formamide by C6F13CH2CH2I (1c) is considerably slower and less efficient than alkylation by 1-bromooctane.This result stands in sharp contrast to fast, efficient reaction of 1c with N-methylformamide or with DMF and water.
- Brace, Neal O.
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p. 1804 - 1811
(2007/10/02)
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- Alkylation Reactions by Means of Alkanols and Carbon Monoxide: An Efficient Synthesis of Thioethers and of Caffeine from Theophylline
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The reaction of sodium or potassium thiolates with alkanols and carbon monoxide provides a versatile route to produce thioethers in excellent yields.By analogy, the potassium salt of theophylline suffers a nearly quantitative conversion to caffeine when heated with methanol under CO pressure.The mechanism of these alkylation reactions is discussed. - Key Words: Nucleophilic alkylation / Thioethers / Caffeine / Carbon monoxide / Alkanols
- Bott, Kaspar
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p. 1955 - 1956
(2007/10/02)
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- Le formamide, un substitut de l'eau dans les reactions d'echange chlore-fluor par transfert de phase solide-liquide
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The fluoride-chloride exchange reaction RCl+KF -> RF+KCl catalysed by ammonium salts, was found to take place in presence of formamide in place of water.The results, depending of RCl are discussed in this paper.
- Escoula, Brigitte,Rico, Isabelle,Lattes, Armand
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p. 256 - 259
(2007/10/02)
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- LE FORMAMIDE, UN SUBSTITUT DE L'EAU XVI 1: REACTIONS D'ECHANGE CHLORE-FLUOR EN TRANSFERT DE PHASE SOLIDE-LIQUIDE
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The chloride-fluoride exchange reaction, RCl+KF -> RF+KCl, catalised by ammonium salts, was found to take place in the presence of formamide when this is used as a replacement for water.The experimental results and their dependence on RCl are discussed in this communication.
- Escoula, B.,Rico, I.,Lattes, A.
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p. 487 - 494
(2007/10/02)
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- Homogeneous Catalytic Synthesis of Alkyl Formates from the Reaction of Alkyl Halides, CO2, and H2 in the Presence of Anionic Group 6 Carbonyl Catalysts and Sodium Salts
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Group 6 metal pentacarbonyl chlorides and bridging hydrides, (CO)5MCl- and (μ-H)- (M = Cr, Mo, or W), have been found to be effective homogeneous catalyst precursors for the production of long chain formate esters (HCO2R, R = n-butyl or n-octyl) from CO2, H2, and alkyl halides (RX; X = Cl, Br, or I) in the presence of alkali-metal salts (NaHCO3, Na2CO3, or K2CO3).For all the catalytic reactions conversions were found to be between 26 and 40percent with respect to RX.The selectivities toward the alkyl formates were found to be higher than 70percent.The only other organic products detected (by GC and GC-IR) were the corresponding alcohols, which were produced by the hydrolysis of the formate esters.The proposed catalytic cycle involves the reaction of (CO)5MCl- with dihydrogen in the presence of sodium salts to produce the terminal hydride (CO)5WH-.The latter complex dimerizes under the reaction conditions with subsequent formation of the bridging hydride (μ-H)-, which was detected in the reaction solution.The terminal hydride rapidly inserts CO2 to produce the formate complex (CO)5MO2CH-, which in turn reacts with the alkyl halide to yield the formate esters and regenerate the halide complex (CO)5MCl-.This latter process is shown to proceed via loss of a carbon monoxide ligand.Subsequent oxidative addition of the alkyl halide to the metal center followed by reductive elimination of alkyl formate, or direct alkylation of the distal oxygen of the carboxylate ligand to afford alkyl formate and the metal halide complex, completes the reaction cycle.The overall process has been found very useful for the synthesis of long-chain alkyl formates starting from inexpensive starting materials such as CO2 and alkyl halides.
- Darensbourg, Donald J.,Ovalles, Cesar
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p. 3330 - 3336
(2007/10/02)
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- One-Pot Conversion of Primary Alkyl Chlorides and Dichlorides into Alcohols, Diols, and Ethers via Formic Ester Intermediates under Phase-Transfer Conditions
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A procedure for the synthesis of alkyl formates, 1,ω-alkanediyl diformates, and unsaturated analogs from alkyl (or 2-alkenyl) halides and sodium formate under solid/liquid phase-transfer conditions is reported.For conversion into alcohols or diols, respectively, the formic esters can be directly hydrolyzed in the reaction mixture of their preparation.Using a related procedure, cyclic ethers are prepared from 1,ω-dichloroalkanes, sodium formate, and potassium hydroxide under solid/liquid phase-transfer conditions.
- Zahalka, Hayder A.,Sasson, Yoel
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p. 763 - 765
(2007/10/02)
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- COMPETITIVE ADDITION OF GLYCOL DIFORMATE AND N-ETHYL-N-(2-FORMYLOXYETHYL) FORMAMIDE TO 1-HEXENE.
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For assessment of the reactivity of 2-substituted ethyl radicals, the authors studied competitive conversions of glycol diformate (I) and N-ethyl-N-(2-formyloxyethyl) formamide (II), initiated by tert-butyl peroxide, at 140 degree . It was found that conversion of equimolar amounts of glycol diformate (I) and N-ethyl-N-(2-formyloxyethyl) formamide (II) in presence of tert-butyl peroxide (III) at 140 degree results in parallel formation of ethyl formate (IV) and N,N-diethylformamide (V). Glycol diformate and N-ethyl-N-(2-formyloxyethyl) formamide add to 1-hexene in presence of tert-butyl peroxide to form octyl formate and N-ethyl-N-octylformamide respectively. 2-(N-Ethylformamido)ethyl radicals are less active than 2-formyloxyethyl in homolytic addition to 1-hexene.
- Germash,Zorin,Lapshova,Zlot-skii,Rakhmankulov
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p. 1104 - 1107
(2007/10/02)
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- RADICAL ADDION OF 1,3-DIOXOLANE TO UNSATURETED COMPOUNDS
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The radical addition of 1,3-dioxolane to 1-hexene and vinyl acetate leads to the formation of 2- and 4-substituted dioxolanes and alkyl formates.The products from the reaction of 1,3-dioxolane with acrylonitrile and dimethyl maleate are 2-alkyl-1,3-dioxolanes.
- Safiev, O. G.,Kruglov, D. E.,Popov, Yu. N.,Zlot-skii, S. S.,Rakhmankulov, D. L.
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p. 997 - 1000
(2007/10/02)
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- Transesterification of olefins
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Olefins may be esterified by reaction with esters of saturated alcohols containing at least two carbon atoms in the presence of a catalytic amount of a tin halide catalyst, the reaction being effected at temperatures ranging from about 0° to about 150° C.
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